Detergent compositions comprising stabilised polyamino acid compounds

ABSTRACT

Detergent compositions comprising polyamino acid compounds and salts thereof are provided. More particularly, detergent compositions containing a polyamino acid compound/protein particle comprising at least one polyamino acid compound coated with at least one protein, detergent compositions containing a polyamino acid compound/protein particle comprising at least one protein coated with at least one polyamino acid compound, and detergent compositions containing a polyamino acid compound/protein agglomerate are provided. The polyamino acid compound/protein particle and/or agglomerate resists degradation of the polyamino acid compound.

FIELD OF THE INVENTION

The present invention relates to the use of polyamino acid containingcompounds and salts thereof in detergent compositions. Moreparticularly, it relates to the use of a polyamino acid, includingpolyaspartic acid, wherein said polyamino acid is in close physicalproximity with a protein so as to protect it from degradation.

BACKGROUND OF THE INVENTION

Polyamino acid agents can be used in detergent compositions as buildersor dispersing agents. Such disclosure is given in EP 454126 whichdescribed polyamino acids, including polyaspartic acid, as biodegradablebuilders/co-builders in the formulation of detergents. The saidpolymers, especially those derived from aspartic acid, glutamic acid andmixtures thereof, are described as resistant to heat, stable to pH, nontoxic, non irritant and entirely biodegradable. However, a problemencountered by such use is the degradability of those polymers understorage and over a period of time. PCT/US93/12090 discloses the use ofpolyamino acid protected from contact with a level of alkalinity aswould cause degradation thereof. The said polyamino acid is providedwith a coating, encapsulated or mixed in the form of an agglomerate orgranulate with at least one other material which is preferably analkaline or alkaline reacting compound. However, research by the presentApplicant has revealed that this kind of protection will also degradeunder storage. This being `partially` due to the enzymatic action andalkaline hydrolysis.

It has now been found that a detergent composition containing adetersive surfactant, at least one polyamino acid compound and at leastone protein wherein said polyamino acid compound and said protein are inclose physical proximity shows enhanced storage stability.

A further advantage to the close physical proximity of said polyaminoacid compound and said protein is the enhanced stability and protectionagainst bleaches.

It is a further object of the present invention to provide a detergentcomposition with effective stain and soil removal performance.

SUMMARY OF THE INVENTION

The present invention relates to a detergent composition containing adetersive surfactant, at least one polyamino acid compound and at leastone protein wherein said polyamino acid compound and said protein are inclose physical proximity.

For the purpose of the present invention, the term close physicalproximity means one of the following:

i) an agglomerate or extrudate in which said polyamino acid compound andsaid protein are in intimate admixture;

ii) a polyamino acid particulate coated with one or more layers whereinat least one layer contains the protein;

iii) a protein coated with one or more layers wherein at least one layercontains the polyamino acid compound.

It has to be understood by close physical proximity that the polyaminoacid compound and the protein are not two separate discrete particles inthe detergent composition.

The polyamino acid compound and the protein mixture may be presentwithin the detergent composition in a form selected from an agglomerate,a granulate, a tablet and mixture thereof.

Also provided herein is a process for producing such mixture in a formof an agglomerate within a detergent composition.

TECHNICAL FIELD OF THE INVENTION

The present invention contemplates dispersant containing detergentcompositions having an excellent storage stability against enzymes aswell as against bleaches. More particularly, it relates to a detergentcomposition containing a detersive surfactant, at least one polyaminoacid compound and at least one protein wherein said polyamino acidcompound and said protein are in close physical proximity.

An essential component for the purpose of the invention is a polyaminoacid compound.

The expression `polyamino acid compound` includes herein not only apolyamino acid as such but also a derivative therof, such as an amide,an ester or a salt. The polyamino acid may be a homopolymer or may be acopolymer of two or more amino acids. The amino acid may be a D-aminoacid, an L-amino acids or a mixture, e.g. a racemic mixture, therof. Theamino acid include, for instance, alanine, glycine, tyrosine, serine andlysine, although glutamic, carboxyglutamic and aspartic acids arepreferred. Of these, aspartic acid is particularly preferred.

Normally, for the purpose of formulating a detergent composition, inparticular a laundry detergent composition, the polyamino acid will beused in the form of a salt therof, preferably an alkali metal salt andmore preferably the sodium salt.

It will be understood that the polyamino acid compound may beconstituted by a mixture of two or more compounds of the appropriatedescription.

The molecular weight of the polyamino acid compound may be varied withinwide limits. Preferably, the molecular weight is from 500 to 200,000,more preferably 2000 to 20,000.

The polyamino acid described herein before will comprise from 10% to90%, preferably from 10% to 40% and more preferably from 10% to 20% byweight of the polyamino acid-protein mixture.

The other essential component useful for the purpose of the invention isa protein which is in intimate contact with the polyamino acid so as toprotect it from attack by enzymes and further by bleaches.

By protein, it is meant any of a class of high molecular-weight polymercompounds composed of a variety of α-amino acids joined by peptidelinkages, excluding those from a group of catalytic proteins that areproduced by living cells and that mediate and promote the chemicalprocesses of life without themselves being altered or destroyed.

Suitable proteins for the purpose of the invention are micro-organisms(yeast, bacteria, mold, etc.) and those proteins extracted therefrom,animal proteins (collagen, gelatin, glue, keratin, casein, egg albumin,etc.) and vegetable proteins (soybean protein, wheat gluten, etc.).

A preferred protein is white egg albumin.

The protein described herein before will comprise from 10% to 90%,preferably from 10% to 40% and more preferably from 10% to 20% by weightof the polyamino acid-protein mixture.

According to the present invention, a polyamino acid compound isstabilised against degradation sufficiently to render it acceptablystorage-stable. This is effected, in particular, by protecting the saidcompound from contact with enzymes, bleaches and high alkalinity. Saidstabilisation may be obtained by admixing to said polyaspartate aprotein such as described herein before wherein said polyamino acidcompound and said protein are in close physical proximity (e.g. theprotein is admixed to the polyamino acid in a such intimate contact thatthe enzymes, source of damage for said polyamino acid, willpreferentially and selectively attack the protein instead of thepolyamino acid compound).

Another advantage to said mixture is the further protection of saidpolyamino acid against bleaches and high alkalinity which have also beenshown as being detrimental to the stability of said polyamino acid uponstorage.

The stabilisation or protection should be such that the amount ofdegradation of the polyamino acid compound in the detergent compositionis less than 50% over a 4 week storage period under stressed conditions(90° F. (32.2° C.) and 80% relative humidity) and preferably less than30%.

Further components may be admixed to said mixture. Suitable componentsare those having no deleterious effect on the mixture properties so thatthe amount of degradation of the polyamino acid remains as specifiedherein before.

Suitable components which may be admixed to said mixture are carbonates(including bicarbonates), sulphates and aluminosilicates.

Another preferred embodiment suitable for the purpose of the inventioncomprises agglomerates formed from the polyamino acid and the proteinmixture and contained in such detergent composition to enhancestabilisation. Other components may, of course, be included in suchagglomerates. The agglomeration of the polyamino acid compound and theprotein may be carried out using any suitable agglomeration techniqueand apparatus, if appropriate with compatible agglomeration auxiliaries.Such techniques, apparatus and auxiliaries are well-known in thedetergent formulating art. Once the agglomerates are formed, they may bedried, if required, by conventional means.

A suitable process for producing a detergent composition, containingsaid polyamino acid-protein mixture in the form of an agglomerate,comprises the steps of:

a--contacting said protein with said polyamino acid in the presence ofwater,

b--agitating the resulting mixture so as to obtain a solid brittleagglomerate,

c--grinding said agglomerate so as to obtain a size of from 250 μm to800 μm,

d--incorporating the agglomerate in the detergent composition.

A typical agglomerate formulation comprises:

    ______________________________________    Polyamino acid compound                           10 to 90%    Protein                10 to 40%    ______________________________________

The molten materials, viz the polyamino acid compound and the proteinagglomerating agent are fed to the agglomerator at a temperature between35° C. and 40° C. The resulting mass is then mixed for a further 3 hoursuntil a yellow/browned color paste is formed. The mixing is then stoppedand the paste is left in an oven at 35° C. for 24 hours. The resultingsolid is crushed in a mortar and pestle to a fine powder. The product isthen sieved and materials that are greater than 800 micrometers andsmaller than 250 micrometers are removed.

The stabilised polyamino acid (e.g. the polyamino acid-protein mixture)according to the present invention is used as a dispersing agent (whichterm includes a clay-soil-suspending agent and/or an anti-redepositionagent) in solid (e.g. granular or other particulate) detergentcompositions and will generally be employed therein at a level of from0.1% to 50%, usually at least 0.4%, preferably 1 to 15%, more preferably1% to 10% and most preferably 2.5% to 5.5% by weight of the detergentcomposition.

The polyamino acid-protein mixture will usually have a weight ratio ofsaid polyamino acid to said protein of from 9:1 to 1:9, preferably from4:1 to 1:4 and more preferably from 2:1 to 1:2.

Although the polyamino acid-protein mixture may be included in a widevariety of cleaning compositions, for example hard-surface and otherhousehold cleaners and dishwashing compositions, they are particularlysuitable for use in laundry detergent compositions, e.g. general-purposeor heavy-duty laundry detergent compositions. These will contain notonly the stabilised polyamino acid compound-protein mixture anddetersive surfactant but also, optionally, one or more furthercomponents conventional in the art; these may be selected from, forexample, a detergent builder, a bleach (in particular a source ofhydrogen peroxide, e.g. sodium perborate or sodium percarbonate), ableach activator, an enzyme, a polymeric soil-release agent, a chelatingagent, a conventional dispersing agent, a brightener, a suds suppressor,a pH-buffering agent, a dye, a dye transfer inhibition agent or apigment. It will be understood that any of the above-mentionedcomponents, whether essential or optional, may be constituted, ifdesired, by a mixture of two or more compounds of the appropriatedescription.

Detersive Surfactants

The total amount of surfactants will be generally up to 70%, typically 1to 55%, preferably 1 to 30%, more preferably 5 to 25% and especially 10to 20% by weight of the total composition.

Nonlimiting examples of surfactants useful herein include theconventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") and primary,branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), the C₁₀ -C₁₈secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x) (CHOSO₃ ⁻M⁺) CH₃ and CH₃ (CH₂)_(y) (CHOSO₃ ⁻ M⁺) CH₂ CH₃ where x and (y+1) areintegers of at least 7, preferably at least 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates ("AE_(x) S";especially EO 1-7 ethoxy sulfates), C₁₀ -C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers,the C₁₀ -C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, and C₁₂ -C₁₈ alpha-sulfonated fatty acid esters. Ifdesired, the conventional nonionic and amphoteric surfactants such asthe C₁₂ -C₁₈ alkyl ethoxylates ("AE"), including the so-called narrowpeaked alkyl ethoxylates and C₆ -C₁₂ alkyl phenol alkoxylates(especially ethoxylates and mixed ethoxy/propoxy), C₁₂ -C₁₈ betaines andsulfobetaines ("sultaines"), C₁₀ -C₁₈ amine oxides, and the like, canalso be included in the overall compositions. The C₁₀ -C₁₈ N-alkylpolyhydroxy fatty acid amides can also be used. Typical examples includethe C₁₂ -C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such asC₁₀ -C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀ -C₂₀ conventional soapsmay also be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆ soaps may be used. Other suitable surfactants suitable for thepurpose of the invention are the anionic alkali metal sarcosinates offormula:

    R-CON(R.sup.1)CH.sub.2 COOM

wherein R is a C₉ -C₁₇ linear or branched alkyl or alkenyl group, R¹ isa C₁ -C₄ alkyl group and M is an alkali metal ion. Preferred examplesare the lauroyl, cocoyl (C₁₂ -C₁₄), myristyl and oleyl methylsarcosinates in the form of their sodium salts.

Mixtures of anionic and nonionic surfactants are especially useful.Other conventional useful surfactants are listed in standard texts.

Adjunct Ingredients

The compositions herein can optionally include one or more otherdetergent adjunct materials or other materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the detergent composition (e.g.,perfumes, colorants, dyes, etc.). The following are illustrativeexamples of such adjunct materials.

Builders--Detergent builders can optionally be included in thecompositions herein to assist in controlling mineral hardness. Inorganicas well as organic builders can be used. Builders are typically used infabric laundering compositions to assist in the removal of particulatesoils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form.

Granular formulations typically comprise from 10% to 80%, more typicallyfrom 15% to 50% by weight, of the detergent builder. Lower or higherlevels of builder, however, are not meant to be excluded.

Inorganic or phosphate-containing detergent builders include, but arenot limited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates).

Non-phosphate builders may also be used. These can include, but are notrestricted to phytic acid, silicates, alkali metal carbonates (includingbicarbonates and sesquicarbonates), sulphates, aluminosilicates,monomeric polycarboxylates, homo or copolymeric polycarboxylic acids ortheir salts in which the polycarboxylic acid comprises at least twocarboxylic radicals separated from each other by not more than twocarbon atoms, organic phosphonates and aminoalkylene poly (alkylenephosphonates). The compositions herein also function well in thepresence of the so-called "weak" builders (as compared with phosphates)such as citrate, or in the so-called "underbuilt" situation that mayoccur with zeolite or layered silicate builders.

Examples of silicate builders are the so called `amorphous` alkali metalsilicates, particularly those having a SiO₂ :Na₂ O ratio in the range1.6:1 to 3.2:1 and crystalline layered silicates, such as the layeredsodium silicates described in U.S. Pat. No. 4,664,839. NaSKS-6 is thetrademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, theNaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂ Si₂ O₅ morphology form of layered silicate. It can be preparedby methods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x) O_(2x+1).yH₂ O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used herein. Various other layeredsilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as thealpha, beta and gamma forms. As noted above, the delta-Na₂ Si₂ O₅(NaSKS-6 form) is most preferred for use herein. Other silicates mayalso be useful such as for example magnesium silicate, which can serveas a crispening agent in granular formulations, as a stabilizing agentfor oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    Na.sub.z  (AlO.sub.2).sub.z (SiO.sub.2).sub.y !.xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to 0.5, and x is an integer from 15 to 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturallyoccurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669. Preferredsynthetic crystalline aluminosilicate ion exchange materials usefulherein are available under the designations Zeolite A, Zeolite P (B),Zeolite MAP and Zeolite X. In an especially preferred embodiment, thecrystalline aluminosilicate ion exchange material has the formula:

    Na.sub.12  (AlO.sub.2).sub.12 (SiO.sub.2).sub.12 !.xH.sub.2 O

wherein x is from 20 to 30, especially 27. This material is known asZeolite A. Dehydrated zeolites (x=0-10) may also be used herein.Preferably, the aluminosilicate has a particle size of 0.1-10 microns indiameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in U.S. Pat. No. 3,128,287 and U.S. Pat. No. 3,635,830. Seealso "TMS/TDS" builders of U.S. Pat. No. 4,663,071. Suitable etherpolycarboxylates also include cyclic compounds, particularly alicycliccompounds, such as those described in U.S. Pat. Nos. 3,923,679;3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether or acrylic acid, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, thevarious alkali metal, ammonium and substituted ammonium salts ofpolyacetic acids such as ethylenediamine tetraacetic acid andnitrilotriacetic acid, as well as polycarboxylates such as melliticacid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and solublesalts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984. Useful succinic acid buildersinclude the C₅ -C₂₀ alkyl and alkenyl succinic acids and salts thereof.A particularly preferred compound of this type is dodecenylsuccinicacid. Specific examples of succinate builders include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Laurylsuccinates are thepreferred builders of this group, and are described in EP 0,200,263.

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226and in U.S. Pat. No. 3,308,067. See also U.S. Pat. No. 3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for handlaunderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Bleaching Compounds--Bleaching Agents and Bleach Activators--Thedetergent compositions herein may optionally contain bleaching agents orbleaching compositions containing a bleaching agent and one or morebleach activators. When present, bleaching agents will typically be atlevels of from 0.1% to 60%, more typically from 1% to 30% and morepreferably from 5% to 20% by weight, of the detergent composition,especially for fabric laundering.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.The bleaching agent, source of alkaline hydrogen peroxide in the washliquor, is an inorganic perhydrate bleach normally in the form of thesodium or magnesium salt.

The perhydrate may be any of the alkali inorganic salts such asperborate monohydrate or tetrahydrate, percarbonate, perphosphate andpersilicate salts, but is conventionally an alkali metal perborate orpercarbonate. Sodium percarbonate, which is the preferred perhydrate, isan addition compound having a formula corresponding to 2Na₂ CO₃.3H₂ O₂,and is available commercially as a crystalline solid. Most commerciallyavailable material includes a low level of a heavy metal sequestrantsuch as EDTA, 1-hydroxyethylene 1,1-diphosphonic acid (HEDP) or anaminophosphonate, that is incorporated during the manufacture process.For the purposes of the detergent composition aspect of the invention,the percarbonate can be incorporated into detergent compositions withoutadditional protection, but preferred executions of such compositionsutilise a coated form of the material. A variety of coatings can be usedincluding borosilicate borate, boric acid and citrate or sodium silicateof SiO₂ :Na₂ O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied asan aqueous solution to give a level of from 2% to 10%, (normally from 3%to 5%) of silicate solids by weight of the percarbonate. However themost preferred coating is a mixture of sodium carbonate and sulphate orsodium chloride.

The particle size range of the crystalline percarbonate is from 350micrometers to 1 500 micrometers with a mean of approximately 500-1000micrometers.

Another category of bleaching agent that can be used in place of or incombination with the mixture of an inorganic perhydrate and a bleachactivator encompasses the preformed peracid bleaching agents and saltsthereof. Suitable examples of this class of agents include(6-octylamino)-6-oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid,(6-decylamino)-6-oxo-caproic acid, magnesium monoperoxyphthalatehexahydrate, the magnesium salt of metachloro-perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.Pat. No. 4,634551, EP 0,133,354, U.S. Pat. No. 4,412,934 and EP0,170,386.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. The amount of bleachactivators will typically be from 0.1% to 60%, more typically from 0.5%to 40% by weight of the detergent composition.

Various nonlimiting examples of activators are disclosed in U.S. Pat.No. 4,915,854 and U.S. Pat. No. 4,412,934. The nonanoyloxybenzenesulfonate (NOBS), isononanoyloxybenzene sulfonate (ISONOBS) andtetraacetyl ethylene diamine (TAED) activators are typical, and mixturesthereof can also be used.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from 6 to 12 carbon atoms, R² isan alkylene containing from 1 to 6 carbon atoms, R⁵ is H or alkyl, aryl,or alkaryl containing from 1 to 10 carbon atoms, and L is any suitableleaving group. A leaving group is any group that is displaced from thebleach activator as a consequence of the nucleophilic attack on thebleach activator by the perhydrolysis anion. A preferred leaving groupis phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed in U.S. Pat. No. 4,966,723. A highly preferredactivator of the benzoxazin-type is: ##STR1##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR2## wherein R⁶ is H or an alkyl, aryl, alkoxyaryl,or alkaryl group containing from 1 to 12 carbon atoms. Highly preferredlactam activators include benzoyl caprolactam, octanoyl caprolactam,3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoylcaprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoylvalerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.See also U.S. Pat. No. 4,545,784 which discloses acyl caprolactams,including benzoyl caprolactam, adsorbed into sodium perborate.

Another class of preferred bleach activators include the cationic bleachactivators, derived from the valerolactam and acyl caprolactamcompounds, of formula: ##STR3## wherein x is 0 or 1, substituents R, R'and R" are each C10 alkyl or C2-C4 hydroxy alkyl groups, or (C_(y)H_(2y))O!_(n) --R'" wherein y=2-4, n=1-20 and R'" is a C1-C4 alkyl groupor hydrogen and X is an anion.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718. If used, detergent compositions will typicallycontain from 0.025% to 1.25%, by weight, of such bleaches, especiallysulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. 5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416;U.S. Pat. No. 5,114,606; and EP 549,271A1, 549,272A1, 544,440A2, and544,490A1; Preferred examples of these catalysts include Mn^(IV) ₂(u-O)₃ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂(u-O)₁ (u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₂,Mn^(IV) ₄ (u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄(u-O)₁ (u-OAc)₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃,Mn^(IV) -(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. Theuse of manganese with various complex ligands to enhance bleaching isalso reported in the following U.S. Pat. Nos.: 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from 0.1 ppm to 700ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species inthe laundry liquor.

Chelating Agents--The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Preferred biodegradable non-phosphorus chelants for use herein areethylenediamine disuccinate ("EDDS"), especially the S,S! isomer asdescribed in U.S. Pat. No. 4,704,233, ethylenediamine-N,N'-diglutamate(EDDG) and 2-hydroxypropylene-diamine-N,N'-disuccinate (HPDDS)compounds.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) available under thetrademark DEQUEST from Monsanto. Preferably, these amino phosphonates donot contain alkyl or alkenyl groups with more than 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044. Preferredcompounds of this type in acid form are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

If utilized, these chelating agents will generally comprise from 0.1% to10% by weight of the detergent compositions herein. More preferably, ifutilized, the chelating agents will comprise from 0.1% to 3.0% by weightof such compositions.

Enzymes--Enzymes can be included in the formulations herein for a widevariety of fabric laundering purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains, forexample, for the prevention of fugitive dye transfer, and for fabricrestoration. The enzymes to be incorporated include proteases, amylases,lipases, cellulases, and peroxidases, as well as mixtures thereof. Othertypes of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.However, their choice is governed by several factors such as pH-activityand/or stability optima, thermostability and stability versus activedetergents and builders. In this respect bacterial or fungal enzymes arepreferred, such as bacterial amylases and proteases, and fungalcellulases.

Enzymes are normally incorporated at levels sufficient to provide up to5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme pergram of the composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE. The preparationof this enzyme and analogous enzymes is described in GB 1,243,784 ofNovo. Proteolytic enzymes suitable for removing protein-based stainsthat are commercially available include those sold under the tradenamesALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE byInternational Bio-Synthetics, Inc. (The Netherlands). Other proteasesinclude Protease A (see EP 130,756) and Protease B (see EP 257,189).

Amylases include, for example, α-amylases described in GB1,296,839(Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, NovoIndustries. FUNGAMYL (Novo) is especially useful.

The cellulase usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,which discloses fungal cellulase produced from Humicola insolens andHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk (Dolabella Auricula Solander). suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.ENDO A, CAREZYME both from Novo Industries A/S are especially useful.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.1 54, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open to public inspection on Feb. 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd.,Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P." Other commercial lipases include Amano-CES,lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicolalanuginosa and commercially available from Novo (see also EP 0,341,947)is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching," i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813 assigned to NovoIndustries A/S.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139. Enzymes are further disclosed in U.S. Pat. No. 4,101,457 andin U.S. Pat. No. 4,507,219. Enzyme materials useful for liquid detergentformulations, and their incorporation into such formulations, aredisclosed in U.S. Pat. No. 4,261,868. Enzymes for use in detergents canbe stabilized by various techniques. Enzyme stabilization techniques aredisclosed and exemplified in U.S. Pat. No. 3,600,319 and EP 0 199 405.Enzyme stabilization systems are also described, for example, in U.S.Pat. No. 3,519,570.

Enzyme Stabilizers--The enzymes employed herein are stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions which provide such ions to the enzymes.(Calcium ions are generally somewhat more effective than magnesium ionsand are preferred herein if only one type of cation is being used.)Additional stability can be provided by the presence of various otherart-disclosed stabilizers, especially borate species: see Severson, U.S.Pat. No. 4,537,706. The level of calcium or magnesium ions should beselected so that there is always some minimum level available for theenzyme, after allowing for complexation with builders, fatty acids,etc., in the composition. Any water-soluble calcium or magnesium saltcan be used as the source of calcium or magnesium ions, including, butnot limited to, calcium chloride, calcium sulfate, calcium malate,calcium maleate, calcium hydroxide, calcium formate, and calciumacetate, and the corresponding magnesium salts. A small amount ofcalcium ion, generally from 0.05 to 0.4 millimoles per liter, is oftenalso present in the composition due to calcium in the enzyme slurry andformula water. In solid detergent compositions the formulation mayinclude a sufficient quantity of a water-soluble calcium ion source toprovide such amounts in the laundry liquor. In the alternative, naturalwater hardness may suffice.

It is to be understood that the foregoing levels of calcium and/ormagnesium ions are sufficient to provide enzyme stability. More calciumand/or magnesium ions can be added to the compositions to provide anadditional measure of grease removal performance. Accordingly, as ageneral proposition the compositions herein will typically comprise from0.05% to 2% by weight of a water-soluble source of calcium or magnesiumions, or both. The amount can vary, of course, with the amount and typeof enzyme employed in the composition.

The compositions herein may also optionally, but preferably, containvarious additional stabilizers, especially borate-type stabilizers.Typically, such stabilizers will be used at levels in the compositionsfrom 0.25% to 10%, preferably from 0.5% to 5%, more preferably from0.75% to 3%, by weight of boric acid or other borate compound capable offorming boric acid in the composition (calculated on the basis of boricacid). Boric acid is preferred, although other compounds such as boricoxide, borax and other alkali metal borates (e.g., sodium ortho-, meta-and pyroborate, and sodium pentaborate) are suitable. Substituted boricacids (e.g., phenylboronic acid, butane boronic acid, and p-bromophenylboronic acid) can also be used in place of boric acid.

Other Ingredients

A wide variety of other functional ingredients commonly used indetergent compositions can be included in the compositions of thepresent invention. These include additional clay soilremoval/anti-redeposition agents, polymeric soil release agents, dyetransfer inhibiting agents, brighteners, suds suppressors and fabricsofteners. Suitable additional clay soil removal/anti-redepositionagents may include acrylic/maleic based copolymers, polyethylene glycol(PEG), water-soluble ethoxylated amines and carboxy methyl cellulose(CMC).

Other ingredients useful in detergent compositions can be included inthe compositions herein, including other active ingredients, carriers,hydrotropes, processing aids, dyes or pigments, solvents for liquidformulations, solid fillers for bar compositions, etc. If high sudsingis desired, suds boosters such as the C₁₀ -C₁₆ alkanolamides can beincorporated into the compositions, typically at 1%-10% levels. The C₁₀-C₁₄ monoethanol and diethanol amides illustrate a typical class of suchsuds boosters. Use of such suds boosters with high sudsing adjunctsurfactants such as the amine oxides, betaines and sultaines noted aboveis also advantageous. If desired, soluble magnesium salts such as MgCl₂,MgSO₄, and the like, can be added at levels of, typically, 0.1%-2%, toprovide additional suds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned photoactivators, dyes, fluorescers, fabricconditioners and hydrolyzable surfactants can be "protected" for use indetergents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups(e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol)can also be used. The compositions may contain from 5% to 90%, typically10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Liquiddishwashing product formulations preferably have a pH between 6.8 and9.0. Laundry products are typically at pH 9-11. Techniques forcontrolling pH at recommended usage levels include the use of buffers,alkalis, acids, etc., and are well known to those skilled in the art.

The bulk density of granular detergent compositions is typically atleast 450 g/liter, more usually at least 600 g/liter and more preferablyfrom 650 g/liter to 1000 g/liter.

The invention is illustrated in the following non limiting examples, inwhich all percentages are on a weight basis unless otherwise stated.

In the detergent compositions, the abbreviated component identificationshave the following meanings:

    ______________________________________    LAS          Sodium linear C.sub.12 alkyl benzene                 sulphonate    TAS          Sodium tallow alkyl sulphate    XYAS         Sodium C.sub.1X -C.sub.1Y alkyl sulphate    C24EY        A C.sub.12-14 predominantly linear primary                 alcohol condensed with an average of Y                 moles of ethylene oxide    C25EY        A C.sub.12-15 predominantly linear primary                 alcohol condensed with an average of Y                 moles of ethylene oxide    C45EY        A C.sub.14 -C.sub.15 predominantly linear primary                 alcohol condensed with an average of Y                 moles of ethylene oxide    CXYEZS       C.sub.1X -C.sub.1Y sodium alkyl sulphate                 condensed with an average of Z moles of                 ethylene oxide per mole    polyhydroxy fatty                 N-Lauroyl N-Methyl Glucamine    acid amide    NaSKS-6      Crystalline layered silicate of formula                 δ-Na.sub.2 Si.sub.2 O.sub.5    PAS          Polyaspartic acid of molecular weight in                 the range of 500 to 200,000    Carbonate    Anhydrous sodium carbonate    Silicate     Amorphous sodium silicate (SiO.sub.2 :Na.sub.2 O                 ratio normally follows)    MA/AA        Copolymer of 1:4 maleic/acrylic acid,                 average molecular weight about 70,000    Zeolite A    Hydrated Sodium Aluminosilicate of                 formula Na.sub.12  (AlO.sub.2)(SiO.sub.2)!.sub.12.27H.sub.2                 O                 having a primary particle size in the range                 from 1 to 10 micrometers    Photobleach  Tetra sulphonated zinc phthalocyanine    Citrate      Tri-sodium citrate dihydrate    Citric acid  Anhydrous Citric Acid    PB1          Sodium perborate monohydrate bleach of                 nominal formula NaBO.sub.2.H.sub.2 O.sub.2    PB4          Sodium perborate tetrahydrate bleach of                 nominal formula NaBO.sub.2.H.sub.2 O.sub.2.3H.sub.2 O    Percarbonate Anhydrous sodium percarbonate bleach of                 empirical formula 2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2                 coated                 with a mixed salt of formula                 Na.sub.2 SO.sub.4.n.Na.sub.2 CO.sub.3 where n is 0.29 and                 where the weight ratio of percarbonate to                 mixed salt is 39:1    TAED         Tetraacetyl ethylene diamine    Savinase     Proteolytic enzyme activity 4 KNPU/g    Alcalase     Proteolytic enzyme activity 3.3 AU/g    Lipolase     Lipolytic enzyme activity 100 KLU/g    Cellulase    Cellulytic enzyme activity 1000 SCEVU/g    Endo A       Cellulytic enzyme activity 5000 SCEVU/g    all sold by NOVO Industries A/S    PVNO         Polyvinyl pyridine N-oxide polymer of                 molecular weight 10,000    PVPVI        Polyvinyl pyrrolidone-co-imidazole)                 polymer of molecular weight in the range                 of 100 to 1000000    MgSO4        Anhydrous Magnesium Sulphate    SRP          modified anionic polyester Soil Release                 Polymer    CMC          Sodium carboxymethyl cellulose    EDDS         Ethylenediamine-N,N'-disuccinic                 acid,  S,S! isomer in the form of the                 sodium salt.    Brightener   Disodium 4,4'-bis-(2-sulphostyryl)-                 biphenyl.    DETPMP       Diethylenetriamine penta (Methylene                 phosphonic acid) marketed by                 Monsanto under the Trade name                 Dequest 2060.    Mixed Suds   25% paraffin wax Mpt 50° C., 17%    suppressor   hydrophobic silica, 58% paraffin oil.    ______________________________________

EXAMPLE 1 Preparation of the Polyamino Acid-Protein AgglomerateContained in a Detergent Composition.

100 g of a polyaspartic acid solution (25% active) was mixed with 20 gof albumin (100% active) in a round bottom flask. The resulting mixturewas then stirred for a further 3 hours at a temperature between 35° C.and 40° C. at a paddle speed of 1 50 r.p.m, until a yellow/brownedcoloured paste formed. The mixing was then stopped and the paste wasleft in an oven at 35° C. for a further 24 hours. The resulting solidwas crushed using a mortar and pestle into a fine powder (yellow/brownin color). The product was then sieved and materials that were greaterthan 800 microns and smaller than 250 microns were removed. Theremaining material was used in the testing.

4.8% by weight of said polyaspartic acid/albumin agglomerate was takenand incorporated in a nil dispersant detergent matrix (100 g). The nildispersant detergent matrix had the following composition in % byweight:

    ______________________________________    45AS                 6.84    C25E3S               1.71    C24E5                3.37    polyhydroxy fatty acid amide                         1.45    Zeolite A            10.19    Citric               2.45    SKS-6                9.0    Carbonate            5.38    CMC                  0.30    SRP                  0.20    PVNO                 0.02    Savinase             0.69    Lipolase             0.18    Cellulase            0.20    Endo A               0.25    Termamyl             0.6    TAED                 3.75    DETPMP               0.6    MgSO4                0.6    Percarbonate         16.9    Brightener           0.22    Photoactivated bleach                         0.002    Suds suppressor      2.75    Perfume              0.35    Water minors and miscellaneous    to balance    ______________________________________

Storage stability results of the polyaspartic acid-albumin agglomeratecontained in a detergent composition vs a pure polyaspartate granulecontained in a detergent composition after a 4 week storage period understressed conditions (90° F. (32.2° C.) and 80% relative humidity).

A comparative composition was prepared containing 4% by weight of thepolyaspartic acid granule and incorporated in 100 g of the herein beforedescribed nil dispersant detergent matrix.

The storage stability analysis was carried out on the stored product,after a 4 week storage period under stressed conditions (90° F. (32.2°C.) and 80% relative humidity), using HPLC. The results are as follows:

    ______________________________________    polyaspartic acid/albumin    agglomerate     polyaspartic acid granule    ______________________________________    80%             50%    ______________________________________

It can be seen that the polyaspartic acid/albumin agglomerate containedin the detergent composition shows enhanced storage stability over thepolyaspartic acid granule contained in the same detergent composition.

EXAMPLE 2

The following detergent compositions were prepared (parts by weight).Compositions A, B, C, D, E are in accordance with the present invention,wherein the polyaspartic acid/albumin agglomerate is as defined inExample 1 and composition F is a comparative composition wherein thepolyaspartic acid/albumin agglomerate is replaced with a maleicacid/acrylic acid copolymer supplied by BASF.

    ______________________________________                 A    B      C      D    E    F    ______________________________________    LAS            --     --     6.54 6.92 6.92 --    TAS            --     --     2.94 2.05 2.05 --    45AS           6.84   6.86   --   --   --   6.84    C25E3S         1.71   1.71   0.16 0.16 0.16 1.71    C45E7          --     --     4.0  4.0  5.0  --    C24E5          3.37   --     --   --   --   3.37    C25E5          --     2.21   --   --   --   --    C25E3          --     1.16   --   --   3.0  --    polyhydroxy fatty acid                   1.45   1.45   --   --   --   1.45    amide    Zeolite A      10.19  10.2   18.0 20.2 26.0 10.19    Citrate        --     --     --   5.5  10.4 --    Citric         2.45   2.3    2.35 --   --   2.45    SKS-6          9.0    8.5    8.64 --   --   9.0    PAS-albumin agglomerate                   4.8    4.8    4.8  4.8  4.8  --    Carbonate      5.38   9.8    16.0 15.4 11.9 5.38    Silicate (2.0 ratio)                   --     --     0.56 3.0  2.0  --    Bicarbonate    --     --     4.6  --   6.0  --    Sulphate       --     8.0    --   --   4.8  --    MA/AA          --     3.0    --   --   4.6  4.0    CMC            0.30   0.30   0.30 0.30 0.30 0.30    SRP            0.20   0.15   0.20 0.30 0.30 0.20    PVPVI          --     --     --   0.01 0.04 --    PVNO           0.02   --     --   0.01 0.04 0.02    Savinase       0.69   0.25   0.37 1.4  --   0.69    Alcalase       --     --     --   --   0.55 --    Lipolase       0.18   0.07   0.22 0.36 0.25 0.18    Cellulase      0.20   --     --   --   0.13 0.20    Endo A         0.25   0.12   0.13 0.13 --   0.25    Termamyl       0.6    --     --   --   --   0.6    PB4            --     --     --   11.64                                           --   --    PB1            --     --     --   8.7  --   --    TAED           3.75   1.6    --   5.0  --   3.75    DETPMP         0.6    --     4.8  0.38 0.6  0.6    MgSO4          0.6    0.38   0.4  0.40 --   0.6    Percarbonate   16.9   10.0   17.5 --   --   16.9    EDDS           --     0.21   0.21 --   --   --    Brightener     0.22   0.18   0.19 0.19 --   0.22    Photoactivated bleach                   0.002  0.002  0.002                                      0.002                                           --   0.002    Suds suppressor                   2.75   2.75   0.85 0.85 1.0  2.75    Perfume        0.35   0.4    0.35 0.43 0.35 0.35    Water minors and    miscellaneous to balance    ______________________________________     Compositions A to E were all seen to have a good polyaspartic acid storag     stability.

Test Protocol--Stain Removal

Four white cotton sheets were prewashed in a nil polymer detergentmatrix of density ca 700 mg/liter. 10 stains were then applied to onesheet, 10 stains to the second sheet, 10 stains to the third one and 10to the fourth one. Sets of eight test swatches of size 10 cm×10 cmsquared were cut from each sheet.

The sets of fabric swatches were subjected to one wash cycle in anautomatic washing machine(Miele type short wash cycle). The swatcheswere then assessed for removal of the particulate, greasy, enzymatic andbleachable stains using a well-established lightness measurement method.

In more detail, a Miele 756 WM automatic washing machine was employed,and the 90° C. short cycle programme selected. Water of 25° Germanhardness (=3.75 mol Ca²⁺ /liter) was used. 100 g of detergent, dispensedfrom a granulette dispensing device was employed. One swatch of eachfabric type was washed along with a ballast load of 2.6 Kg of lightlysoiled sheets.

Stain removal was assessed by making LAB (lightness) measurements usingthe X-rite (tradename) color eye spectrophotometer. An unstained cottonsheet was used as the reference. A stain removal index, ΔR, wascalculated as follows:

    ΔR= (L.sub.washed -L.sub.unwashed)/(L.sub.unwashed -L.sub.reference)!×100

where differences of ΔR below 4% are not significant.

Comparative Testing--Stain Removal

The above test protocol was followed in comparing the efficiency ofCompositions A and F in removing different type of dispersant sensitivestains.

The results obtained were as follows:

    ______________________________________    Average ΔR (%)                        A     F    ______________________________________    Average particulate 57    61    Average greasy      63    57    Average enzymatic   43    45    Average bleachable  55    50    ______________________________________     All results are non significant differences

The stain removal obtained for each of Compositions A and F is shown tobe comparable. Thus the presence of albumin as co-agglomerating agent ofthe polyaspartic acid, in Composition A does not significantlycompromise the stain removal capacity of that Composition versus that ofComposition F.

What is claimed is:
 1. A process for producing a detergent compositioncontaining a detersive surfactant, at least one polyamino acid compoundselected from the group consisting of homopolymers, copolymers of two ormore aminoacids, and mixtures thereof and at least one protein selectedfrom the group consisting of micro-organisms and proteins extractedtherefrom, animal proteins and vegetable proteins; and which comprisesthe steps of:a--contacting said protein with said polyamino acidcompound in the presence of water, b--agitating the resulting mixture soas to obtain a solid brittle agglomerate, c--grinding said agglomerateso as to obtain a particle size of from about 250 μm to about 800 μm,d--incorporating the agglomerate in the detergent composition.
 2. Aprocess according to claim 1, wherein the weight ratio of said polyaminoacid compound to said protein is from about 9:1 to about 1:9.
 3. Aprocess according to claim 2, wherein the weight ratio of said polyaminoacid compound to said protein is from about 4:1 to about 1:4.
 4. Aprocess according to claim 2, wherein said polyamino acid compound isselected from the group consisting of polyaspartic acid and polyglutamicacid.
 5. A detergent composition containing a detersive surfactant, apolyamino acid compound/protein agglomerate comprising at least onepolyamino acid compound and at least one protein, and one or moredetergent components selected from the group consisting of bleachingagents, dye transfer inhibiting agents, fabric softening agents, sudssuppressors, enzymes, chelants, builders, soil release polymers,brighteners and mixtures thereof.
 6. A detergent composition accordingto claim 5 wherein said polyamino acid compound is selected from ahomopolymer or a copolymer of two or more amino acids.
 7. A detergentcomposition according to claim 5 wherein said protein is selected fromthe group consisting of micro-organisms and those proteins extractedtherefrom, animal proteins, vegetable proteins and mixtures thereof. 8.A detergent composition according to claim 5 wherein the weight ratio ofsaid polyamino acid compound to said protein is about 9:1 to about 1:9.9. A detergent composition according to claim 5 wherein said polyaminoacid compound is selected from the group consisting of polyaspartic acidand polyglutamic acid.
 10. A detergent composition containing adetersive surfactant, a polyamino acid compound/protein particlecomprising at least one protein coated with at least one polyamino acidcompound, and one or more detergent components selected from the groupconsisting of bleaching agents, dye transfer inhibiting agents, fabricsoftening agents, suds suppressors, enzymes, chelants, builders, soilrelease polymers, brighteners and mixtures thereof.
 11. A detergentcomposition according to claim 10 wherein said polyamino acid compoundis selected from a homopolymer or a copolymer of two or more aminoacids.
 12. A detergent composition according to claim 10 wherein saidprotein is selected from the group consisting of micro-organisms andthose proteins extracted therefrom, animal proteins, vegetable proteinsand mixtures thereof.
 13. A detergent composition according to claim 10wherein the weight ratio of said polyamino acid compound to said proteinis about 9:1 to about 1:9.
 14. A detergent composition according toclaim 10 wherein said polyamino acid compound is selected from the groupconsisting of polyaspartic acid and polyglutamic acid.